Reaction of 1, 3-butadiene and organic sulfonyl halides

ABSTRACT

Compounds of the formula Yn-R-SO2CH2CH CHCH2X wherein X is Cl or Br; Y is Cl, Br, or nitro; R is alkylene or cycloalkylene of one to six carbon atoms; and n is an integer of 1 to 5, such as 4chlorobut-2-enyl-2&#39;&#39;-chloroethyl sulfone, prepared for example by reaction of halo- or nitro-substituted alkylene or cycloalkylene sulfonyl halide with butadiene. Such compounds are useful as aquatic herbicides, pesticides, and fiber-reactive dyestuff intermediates.

0 United States Patent 1151 3,674,856

Chang et al. 45 J l 4, 1972 s41 REACTION OF 1, S-BUTADIENE AND [56] References Cited ORGANIC SULFONYL HALIDES FOREIGN PATENTS OR APPLICATIONS [72] 9:"? E i g' Dav! 1,409,516 7/1965 France ..260/607 A a as 7 654,544 2/1965 Belgium ..260/607 A [73] Assignee: RAF Corporation, New York, NY.

Primary Examiner-Joseph Rebold [22} Flled: 1969 Assistant ExaminerD. R. Phillips [211 App] No 863 383 Attorney-Samson B. Leavitt and Walter C. Kehm Related 0.8. Application Data ABSTRACT n f 23 Compounds of the formula Y,,-R-SO CH Cl-I=CHCH X [63] i ggg rsgz gg 0 Ser No 605,6 Dec wherein X is C] or Br; Y is Cl, Br, or nitro; R is alkylene or cycloalkylene of one to six carbon atoms; and n is an integer of 1 to 5, such as 4-chlorobut-2-enyl-2'-chl0roethyl sulfone, [52] l i/ prepared for example by reaction of haloor nitro-substituted l l l alkylene or cycloalkylene sulfonyl halide with butadiene, Such 260/543 260/557 260/561 S compounds are useful as aquatic herbicides, pesticides, and fiber reactive dyestuff intermediatesle 0 2 Claims, No Drawings REACTION F 1, B-BUTADIENE AND ORGANIC SULFONYL HALIDES This application is a continuation-in-part of our application Ser. No. 605,623 filed Dec. 29, 1966, and now abandoned.

This invention relates to a new and improved method for reacting an aliphatic sulfonyl halide with l,3-butadiene and to the novel products of such process.

The reaction of l,3-butadiene with methanesulfonyl chloride and with benzene sulfonyl chloride have been reported in J .C.S. 4962 (1964) by Asscher and Vofsi. They employed liquid air to cool the reaction mixture so that air in the reactor could be evacuated by a vacuum pump without vaporizing butadiene and the methylene chloride employed as the reaction medium. The authors reported methylene chloride to be the only solvent for these addition reactions, used triethylamine hydrochloride and acetonitrile apparently as an assistant, complexing and/or solubilizing agent for the cupric chloride catalyst, and employed the disodium salt of ethylenediamine tetraacetic acid for the removal of the copper catalyst from the reaction medium.

These previously reported processes are subject to a number of disadvantages. In view of the specificity of the disclosures, it is not apparent that they would be operative with other organic sulfonyl chlorides. As a matter of fact, a number of such other organic sulfonyl chlorides are insoluble in methylene chloride, although it is recognized that optimum results are generally obtained when the reactants are soluble in the reaction medium. The use of liquid air and evacuation is a troublesome and relatively expensive procedure. Use of triethylamine hydrochloride and acetonitrile to assist, solubilize and/or complex the cupric chloride catalyst, and of a chelating agent such as ethylenediamine tetraacetic acid or its salts for removing the copper catalyst from the reaction mixture is likewise troublesome.

It is an object of this invention to provide a process which will not be subject to one or more of the above disadvantages. Another object of the invention is the provision of novel chemical compounds through use of the aforementioned process. Other objects and advantages will appear as the description proceeds.

The attainment of the above objects is made possible by our discoveries that the use of liquid air and evacuation was not necessary in the foregoing reactions, that the reactions could be carried out without exclusion of air, that copper catalyst could be removed from a methylene chloride reaction medium by evaporating volatiles, dissolving the residue in ether, and washing the ether solution with dilute acid, that methylene chloride was inoperative for reactions involving reactants such as organic sulfonyl chlorides insoluble in methylene chloride, that ether, N-methylpyrrolidone, and N,N-dimethyl-formamide or -acetamide constitute excellent solvents for these reactions because they dissolve the cupric chloride catalyst in addition to one or both reactants whether substituted or not and enable elimination of triethylamine- HCl and acetonitrile, and that these improved solvents further permit removal of the copper catalyst from the reaction mixture with minimal decomposition of the reaction product and without the troublesome use of a chelating agent.

The invention accordingly comprises a method of reacting an organic sulfonyl halide of the formula Y,,-R-SO X, wherein X is C1 or Br, Y is Cl, Br, nitro, COOH, COOR, or

NROCR,; R is H or R; R is alkylene or cycloalkylene of one to six carbon atoms; and n is an integer of l to 5, with 1,3-butadiene without exclusion of air. As a further improvement, the invention comprises carrying out the aforementioned process in an ether, N-methylpyrrolidone, or N,N-dimethylforrnamide or -acetamide reaction medium. When employing ether as the reaction medium, the catalyst is readily removed therefrom upon completion of the reaction by washing with dilute HCl or other acid. When using the water soluble N- methylpyrrolidone, N,N-dimethylformamide or N,N- dimethylacetamide as the reaction medium, removal of copper catalyst and recovery of the desired reaction product are readily accomplished by drowning the final reaction mixture in water to precipitate the reaction product which may then be separated by filtration.

The novel compounds of the present invention are those of the formula I. Y,,-R-SO CH CH=CHCH X wherein X is C1 or Br; Y is Cl Br, nitro, -COOH, -COOR, or NROCR,; R is H or R; R is alkylene or cycloalkylene of one to six carbon atoms; and n is an integer of 1 to 5.

In the above formulas alkylene and cycloalkylene refer to any such saturated divalent straight or branched radical of one to six carbon atoms including methylene to hexylene, cyclopentylene and cyclohexylene; R and R and Y (when n is more than 1) may be the same or different; and the maximum value of n depends on the number of carbon atoms in R, i.e. whether it contains five replaceable C-bonded H atoms.

Representative compounds of the invention include those of the above formula I wherein X is Cl and Y,,-R is 2- chloroethyl, 3-chloropropyl, 2,6-dinitrohexyl, 3-bromo-4- nitrobutyl, 3-carboxypropyl, chloromethyl, 3-carbethoxy-4- chloropentyl, S-acetamidopropyl, 4-(N-methyl)acetamidobutyl, 2(N-methyl)butanoylamidopropyl, 3-chlorosulfolane, and the like, and the corresponding compounds wherein X is Br.

Compounds of the above formula I are prepared by reaction in a suitable reaction medium of an organic sulfonyl halide of the formula Y,,-R-SO X with an approximately equimolar amount of 1,3-butadiene wherein the variables have the values given above, without exclusion of air in the presence of cupric chloride catalyst with triethylamine hydrochloride and acetonitrile as catalyst modifiers-assistants-solvents where required. The catalyst is employed in the usual proportions approximating 0.02 to 2 percent based on the weight of the sulfonyl halide reactant. When ether, N-methylpyrrolidone or N,N-dimethyl-formamide or -acetamide is employed as solvent, the use of the triethylamine hydrochloride and acetonitrile is dispensed with, thus constituting a further ad vantage in using these solvents as reaction medial herein. A still further advantage in the use of ether, N-methyl-pyrrolidone or N,N-dimethyl-formamide or -acetamide as the reaction medium in the present process resides in the facility of recovery and purification with diminished or minimal decomposition of the desired reaction product. Temperatures during the reaction may range from room temperature to the boiling point of the reaction medium, elevated temperatures ranging from about 70 to C. being preferred. Super atmospheric pressures are often desirable, or at least use of pressure tight reaction vessels, particularly when using a volatile solvent such as ether as the reaction medium.

The reaction products described herein are characterized by the presence therein of a radical containing a highly reactive bromine or chlorine atom (X) activated by the adjacent vinyl sulfone linkage. As such, they are highly useful as reactants and intermediates in the production of other compounds and functional agents, in addition to being per se useful as effective herbicides against aquatic weeds and other plant life, pesticides, and the like.

Thus, the products of this invention are effective against aquatic weeds such as duckweed, salvinia, elodea, and potamogeton and the like when added to aqueous bodies containing them in concentrations of about 1 to 15, and generally about 10, p.p.m. (parts per million). In some instances, use of a water miscible mutual solvent such as acetone, alcohol or N- methylpyrrolidone may be employed to facilitate application.

Those products containing another reactive or potentially reactive radical as or in the Y group capable of reacting with a dyestuff molecule are further useful as intermediates in the production of fiber-reactive dyestuffs of any desired type, the reactive group in the resulting dyestuff being that part of the compounds of formula I above bonded to the Y,,-R group. The resulting dyestuffs containing at least one fiber-reactive 4- halo-2-butenylsulfonyl group of the formula S0,CH, CH==CHCH,X, and methods for their production from the compounds disclosed and claimed herein are disclosed in our copending application Ser. No. 605,627 entitled Fiber-Reactive Dyestuffs" filed on Dec. 29, 1966, and now abandoned.

The following examples are only illustrative of this invention and are not to be regarded as limitative. All parts and proportions referred to herein and in the appended claims are by weight unless otherwise indicated.

A. In the examples, when methylene chloride is used as solvent, the volatile material is removed under aspirator vacuum at 40 C. after completion of the reaction. The residue is dissolved in ether and the solution washed with 350 ml. portions of 3N HC 1 and finally with water to remove copper catalyst. The washed ether solution is dried with anhydrous sodium sulfate and decantated. The ether solution after decantation is evaporated under reduced pressure (aspirator) on a steam bath to give the desired product.

B. When ether is used as solvent, triethylamine hydrochloride and acetonitrile are eliminated, and the final reaction medium washed directly with dilute l-lCl in a separatory funnel to remove copper catalyst, followed by the remainder of the procedure A.

C. When N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide are employed as solvent, the final reaction medium is directly poured into 200 ml. of cold water with stirring and the desired precipitated product collected by filtration.

Structures of the products are supported by infrared (IR) analysis showing absorptions at 7.75;}, and 8.82 4. which are characteristic of sulfone groups.

EXAMPLE 1 4-chlorobut-2-enyl 2'-chloroethyl sulfone In a sealed glass tube without exclusion of air, a mixture of 16.3 g. (0.1 mole) of 2-chloroethanesulfonyl chloride, 10.8 g. 0.2 mole) of 1,3-butadiene, 30 ml. of methylene chloride and a solution of 0.14 g. of cupric chloride and 0.2 g. of triethylamine hydrochloride in 2.5 ml. of acetonitrile is heated at 100 C. for 3 hours. The resulting mixture is evaporated under reduced pressure to remove the volatile materials. The residue is dissolved in ether and washed in a separatory funnel with 3N hydrochloric acid and water. The washed solution is dried over sodium sulfate and filtered. The filtrate is distilled to give 21.5 g. of product as an oil, b.p. 178-80 C. (0.1 mm.); 1.5250.

Anal. Calcd for C l-l C10 S: C, 33.19; H, 4.64

Found: C, 33.93, H, 4.74

EXAMPLE 2 a. When the procedure of Example 1 is repeated omitting the triethylamine hydrochloride and acetonitrile, an unsatisfactory yield of about 5 g. of product is obtained.

b. When the foregoing procedure is repeated except for use of ether instead of methylene chloride as solvent and the final reaction mixture directly washed with 3N HCl and water, dried and filtered, an excellent yield of the desired product is obtained.

EXAMPLE 3 4-chlorobut-2-envl 3-chloro-n-propylsulfone C l -CH CH CH -S0 -Cl-l Cl-l=CHCH Cl When 3-chloro-n-propanesulfonyl chloride is used instead of 2-chloroethanesulfonyl chloride in Example 2(b), the

product of the above formula is similarly obtained in good yield.

EXAMPLE 4 4-chlorobut-2-enesulfonyl-n-butyric acid HOOC-CH CH Ch -SO CH CI-ECHCH CI When 4-chlorosu fonyl-n-butyric acid 18 used in Example 2(b) as the sulfonyl chloride, the product of the above formula is similarly obtained in good yield. The corresponding ethyl ester is similarly obtained when using 4-chlorosulfonyl-n-butyric acid ethyl ester as the sulfonyl chloride.

EXAMPLE 5 3-acetamidopropyl 4-chloro-but-2-enylsulfone In a sealed glass tube without exclusion of air, a mixture of 19.85 g. (0.1 mole) of 3-acetamidopropanesulfonyl chloride, 10.8 g. (0.2 mole) of 1,3-butadiene, 20 ml. N-methylpyrrolidone and 0.17 g. of cupric chloride is heated at C. for 3 hours. The mixture is poured into water and the precipitated reaction product filtered off and, if desired after extraction with ether, dried. The product of the above formula is obtained in good yield.

Similar results are obtained when using N,N-dimethylformamide or -acetamide instead of N-methylpyrrolidone as solvent.

EXAMPLE 6 4-chlorobut-2enyl 2'3-dichloropropanysulfone C1CH -CHC1-CH -SO -CH CH=CHCH C1 When 2,3-dichloropropanesulfonyl chloride is used in Example 2(b) as the sulfonyl chloride, the product of the above formula is similarly obtained in good yield. The corresponding 4-chlorobut-2-enyl 2'-nitro-3'-bromopropanylsulfone is similarly obtained when using 2-nitro-3-bromopropanesulfonyl chloride as the sulfonyl chloride.

EXAMPLE 7 When 3-chloro-4-chlorosulfony1 sulfolane is used in Example 2(b) as the sulfonyl chloride, the following compound is obtained in good yield. 

2. A compound as defined in claim 1 wherein X is Cl. 